Detergent composition

ABSTRACT

Detergent compositions which contain compounds bearing one or more sulfhydryl radicals as activators for enzymes which themselves do not contain sulfhydryl groups or disulfide bonds.

Elnited States Patent [72] Inventors Wolfgang Ernst Adam Wemmel, Belgium; Alain Hardy, Paris, France; Arnvid Sverre Roald, Springfield Township, Hamilton County, Ohio; Wahib Nassif Zaki, Brussels, Belgium [21] Appl. No. 874,945

[22] Filed Nov. 7,1969

[45] Patented Dec. 14, 1971 [73] Assignee The Procter & Gamble Company Cincinnati, Ohio [32] Priority Nov. 19, 1968 [3 3] Netherlands [54] DETERGENT COMPOSITION 7 Claims, No Drawings [52] US. Cl 252/89, 195/68, 252/161, 252/D1G. 12 [51] lnt.Cl Clld 7/42 [50] Field of Search 252/89,

DIG. 12; 195/66, 68, 63 D OTHER REFERENCES Sumner et al., Chemistry & Methods of Enzymes (1953) Academic Press, Inc. p. 40 & 82.

Primary Examiner Leon D. Rosdol Assistant ExqminerW. Schulz Allorney-Robert B. Aylor ABSTRACT: Detergent compositions which contain compounds bearing one or more sulfhydryl radicals as activators for enzymes which themselves do not contain sulfhydryl groups or disulfide bonds.

DETERGENT COMPOSITION BACKGROUND OF THE INVENTION 1. Field of the Invention This invention pertains to detergent compositions which contain compounds bearing one or more sulfhydryl radicals as activators for enzymes which themselves do not contain sulfhydryl groups or disulfide bonds.

2. Prior Art It is known that proteolytic enzymes which do contain sulfhydryl groups or disulfide bonds are reactivable by adding a suitable reducing agent. So, e.g., it is known from U.S. Pat. No. 3,019,171 that cysteine an sodium thiosulfate are satisfactory for the activation of proteolytic enzymes containing sulfhydryl groups or disulfide bonds. Proteolytic enzymes" as meant in this patent are represented by vegetable enzymes such as pinguanain, papain, ficin, bromelin, bromelain, and asclepain. From French patent No. 765,063 it is known that activated protease can be used in detergent compositions; the activation is attained through the addition of hydrogen sulfide, thisolulfate or cyanic acid. The proteases utilized are of vegetable origin and also contain sulfhydryl groups or disulfide bonds. Similar disclosures are found in British patent No. 475,880 which refers to detergent compositions containing vegetable enzymes which are reactivatable through the addition of sodium sulfides or polysulfides.

All these prior art references, however, teach that the proteolytic activity of enzymatic detergent compositions can be enhanced through the addition of activators which must be reducing agents. The reason for this is that the enzyme preparations to which these teachings apply are mostly represented by vegetable enzymes and more particularly by papain or its equivalents which, for a long time, were known to be reactivatable by a treatment with a reducing agent. Without being bound to any theory, it is assumed that this enhancement of papainlike enzyme preparations is related specifically to the changes of the oxidative state of the sulfur atoms which are present in the enzyme molecules. So for example, the activity of papain, which has decreased during its manufacture as a result of the oxidation of the active moiety containing cysteine, can be reactivated by an electrolytic reduction or by the addition of reducing agents.

THE INVENTION It has now unexpectedly been found that a marked enzymatic activity enhancement is obtained by the use of detergent compositions with a content of surface-active agents, builders and enzymes, characterized in, that they contain:

from about 0.01 to about l percent by weight of a compound containing one or more sulhydryl groups, and

from about 0.005 to about 4 percent by weight of enzymes which do not contain sulfhydryl groups or disulfide bonds.

This is so much the more surprising as enzymes which do not contain sulfhydryl groups or disulfide bonds are neither readily oxidizable nor reducable. Enzymes encompassed within the scope of this invention can contain sulfur in a form which does not respond readily to an oxidative or reductive treatment as taught in the prior art. An example of this is AL- CALASE bearing a methionine rest which is not likely to be reactivated when submitted to a prior art treatment. The enhancing agents suitable for being incorporated into enzyme containing detergent compositions in accordance with this invention have to hear one or more sulfhydryl groups. They can be substituted by inorganic or organic radicals or by a mixture of both, although, those derived from organic radicals are preferred for various reasons. Among the advantages one can enumerate for the enhancing agents of this invention are their improved odor acceptance and/Or solubility relative to e.g., alkali-, earth-alkali or metal sulfides or polysulfides which are therefore less desirable in detergent compositions.

The enzymatic activity enhancement can be obtained with all commonly known sulfliydryl bearing compounds. The

preferred activators within the scope of this invention are: cysteine hydrochloride, thioglycollic acid esters derived from C fatty alcohols, calcium-thio-glycolate and their equivalents; the particularly preferred activators are: cysteine, thioglycollic acid, thioglycollic acid esters derived from mC, C,, alcohols, thioglycerol, and their equivalents. The activator should preferably be incorporated in an amount from about 0.0l to about 10 percent by weight, calculated on the total detergent composition. The preferred usage range is from about 0.05 weight percent to about 5 weight percent and most preferably from about 0.2 to about 2 weight percent. The enzymatic activity enhancement is not noticeable when less than 0.0] weight percent are incorporated into the detergent formulation while no additional activity synergism can be obtained by adding more than 10 weight percent of the activator compound. The enzymes suitable for use should not contain sulfhydryl groups or disulfide bonds. They can be of any origin although these enzymes are mostly of bacterial Origin. Most of the enzymes of vegetal origin do bear sulfhydryl groups and/or disulfide bonds, e.g., papain. Preferred for use in the detergent compositions of this invention are the enzyme preparations commercially available under the trade names of AL- CALASE," manufactured by Novo Industry A/S, Copenhagen, Denmark and DA-l0," manufactured by Monsanto Chemical Company. ALCALASE is described, in a trade bulletin bearing that name which was published by Novo Industry A/S, as a proteolytic enzyme preparation manufactured by submerged fermentation of a special strain of bacillus .rubtilis.

Similar results are obtained in using any of the following enzyme preparations:

Trade Name Manufacturer Muxatase 2215 Thermoase PS lUO Experimental enzymes from, for example, Arthrobacter sources have also shown similar enhancement with compounds containing one or more sulfhydryl radicals when incorporated into detergent formulations.

The active enzyme is to be used in a quantity of from about 0.005 weight percent to about 4 percent by weight of the composition. Preferred is a quantity of enzymes of from about 0.01 to about 0.02 weight percent.

In addition to the enzymes and the activator, the detergent compositions of this invention can contain the usual mixtures of other ingredients which are currently incorporated into detergent compositions. So, e.g., organic detergents, builders, suds depressors, antiflocculating agents, brighteners, dyes, perfumes and so on can be used.

Examples of suitable detergent compounds for being employed in accordance with the present invention include:

water-soluble soaps such as the sodium, potassium, am-

monium and alkanolammonium salts of higher fatty acids (C -C and, particularly sodium and potassium tallow and coconut soaps.

anionic synthetic non-soap detergents being represented by the water-soluble salts of organic, sulfuric acid reaction products having in their molecular structure an alkyl radical containing from about eight to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Examples of these are the sodium or potassium alkyl sulfates of alcohols derived from tallow or coconut oil; straight or branched chain sodium or potassium alkyl benzene sulfonates, sodium alkyl glyceryl ether sulfonates, sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol and about 1 to 6 moles of ethylene oxide; sodium or potassium alkyl phenol ethylene oxide ether sulfates with l to 10 units of ehtylene oxide per molecule and wherein the alkyl radicals contain from eight to 12 carbon atoms;

the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium or potassium salts of fatty acid amide of a methyl tauride, for example, are derived from coconut oil, sodium and potassium salts of So -sulfonated C (I anonionic synthetic detergents suitable for being used are, e.g., the condensation products of alkylene oxide with an organic hydrophobic compound, higher fatty amides and nonionic detergents having semipolar characteristics. Some examples of these nonionic detergents are defined hereafter:

1. One class of nonionic synthetic detergents is marketed under the tradename of PLURONlC;" they are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.

2. Alkylphenol-polyethylene oxide condensates, being condensation products of alkyl phenols with 5 to 25 moles of ethylene oxide per mole of alkyl phenol.

3. The condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine.

4. Condensation products of aliphatic alcohols with 5 to 30 moles of ethylene oxide per mole of alcohol.

5. The ammonia, monoethanol, and diethanol amides of fatty acids.

6. Long chain tertiary amine oxides such as dimethyldodecylamine oxide and bis-( Z-hydroxyethyl) dodecylamine oxide.

7. Long chain tertiary phosphone oxides such as dimethyldodecylphosphine oxide and dimethyl-( 2- bydroxydodecyl) phosphine oxide.

8. Long chain sulfoxides such as dodecyl methyl sulfoxide and 3-hydroxy tridecyl methyl sulfoxide.

Examples of ampholytic synthetic detergents: sodium-3- dodecylaminopropionate and sodium-3-dodecylaminopropane sulfonate.

Zwitterionic synthetic detergents are for example 3- (N,N-dirnethyl-N-hexadecylammonio) propanel -sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2- hydroxy propanel -sulfonate.

Suitable organic detergents include sodium alkyl benzene sulfonate, sodium alkyl sulfate, and mixtures thereof wherein the alkyl group is of branched or straight chain configuration and contains about l0 to about 18 carbon atoms.

The alkaline builder salts which can be employed in the detergent compositions of the present invention are employed in an amount to provide, for example, a weight ratio of alkaline builder salt to organic detergent of about 20zi to 1:5. These builders can be selected from a wide variety of known inorganic or organic builder salts. Suitable alkaline, inorganic builder salts include the alkali metal carbonates, phosphates, polyphosphates and silicates.

Suitable organic builder salts include the alkali metal, ammonium, and substituted ammonium polyphosphonates, polyacetates, and polycarboxylates.

The polyphosphonates can be represented by the sodium and potassium salts of methylene diphosphonic acid-, ethylene diphosphonic acid-, ethane-l-hydroxy-l,l-diphosphonic acid and of ethanel,l,2-triphosphonic acid. Also suitable are the water-soluble salts of ethane-Z-carboxy-l,l-diphosphonic acid, hydroxymethanediphosphonic acid, carboxyldiphosphonic acid, ethanel hydroxy-l ,1 ,Z-triphosphonic acid, ethane2-hydroxy-l,l ,2-triphosphonic acid, propanel,l ,3,3,-tetraphosphonic acid, propanel ,l ,2,3- tetraphosphonic acid, and propane-l,2,2,3-tetrap hosphonic acid.

Some examples of polyacetate builders suitable for use herein include the water-soluble salts of ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)-ethylenediaminetriacetic acid, N( 2-hydroxyethyl )-nitrilodiacetic acid, diethylenetriaminepentaacetic acid, 1,2-diaminocyclohexanetetracetic acid and nitrilotriacetic acid. The trisodium salts of the above acids are preferably utilized.

The polycarboxylate builder salts suitable for use herein consist of water-soluble salts of polymeric aliphatic polycarboxylic acids as described in US. Pat. No. 3,308,067 which is incorporated herein by reference.

Bleaching compounds should preferably not be used in compositions in accordance with this invention, as there would certainly be a direct interference between the sulfhydryl bearing compounds and the bleaching compounds resulting in a deterioration of the activators before they are able to enhance the enzymatic activity. Bleaching compounds can be added, however, provided they are physically protected from contact with the other ingredients of the detergent composition and particularly from being in contact with the activators. This is possible if they, as an example, are contained in hermetically sealed packages whose walls are made of a material which is only soluble in the laundering solution at a temperature exceeding about 65 C. as they will not interfere with the enzymatic activity enhancement which occurs in a temperature range from about ambient temperature to about 65 C. above which latter temperature the enzymes tend to be deteriorated by heat. Obviously, the same result can be attained when the bleach compounds are coated with a thin-coating of an inert water-soluble material which does not dissolve at a temperature of below 65 C.

The sulfitydryl bearing activators can be incorporated into detergent compositions by any of the techniques known to be satisfactory for this purpose. Examples of the various possibilities which might be applied satisfactorily are enumerated in what follows:

The activators can, as such, or being encapsulated, be drymixed with the finished detergent composition. Obviously, the encapsulation seems to be in order in the event the sulfhydryl bearing compound is represented by a liquid material which is likely to cause lumping to a solid detergent composition and also when the activator (solid or liquid) tends to lose its activity, due to oxidation or for other reasons during a prolonged storage. The encapsulating material should be neutral versus the activator, provide an adequately closed coating and also dissolve in aqueous laundering solutions at ambient temperature. Another possibility of incorporating the activators would be in preparing coagglomerates by spraying water onto mixtures of hydratable carrier with the activator alone or in mixture with the enzymes, Acceptable results are also obtained in spraying a solution of activators on a carrier, or a previously prepared agglomerate of the enzyme and the carrier as described in Belgian patent No. 697,481. It is quite obvious that this latter technique would work as well when a solution containing both the activator and the enzyme are sprayed on the hydratable carrier. The carriers suitable for being utilized should be compatible with the enhancing agents, particularly with respect to storage stability of the activator. Any of these techniques is suitable for preparing the detergent compositions referred to in the examples.

The unexpected enzymatic activity increase resulting from the incorporation of the sulfhydryl containing activators into detergent compositions containing enzymes free of disulfide bonds and sulfhydryl radicals is illustrated by a series of examples.

EXAMPLE I Detergent compositions (a) and (b) having the compositions as indicated hereafter are prepared by conventional spray-drying of all ingredients but the enzyme carrier agglomerate. The latter is prepared separately by spraying a suspension or a solution of the enzyme preparation onto sodium tripolyphosphate, thereby using the technique described in French Pat. No. 1,520,262, and admixed afterwards. The sulfhydryl containing activators are dry mixed with the finished detergent composition.

The stain removal resulting from the soaking and washing tests, as described hereabove, are each time compared to the stain removal resulting from identical tests carried out in the absence of an activator for the enzymatic activity.

The stain removal of the swatches 15 measured with an EEL i t; Spectrophometer (Evans-Electro-selinium Ltd. UK) with Ingredient g a filter number 603. The light reflectance is measured on the w Linear Ci alkylbenzene su1ionate-s0dium salt 8.5 s atches before (X) and f (Y) soakmg anq/or washing Tetra-propylenebenzenesul[mate-sodium salt 27 10 treatment and the percent stain removal (R%) 18 calculated Sodium tripolyphosphate 59 20 Condensation product of tallow alcohol with 11 usmg the following formula moles of ethylene oxide 1 Hydrogenated fatty acids (CM-C13) 2 Sodium sulfate 13 29 Sodium tripolyphosphate used as carrier for R Y X 100 enzymes 7 7 15 Enzyme preparation (ALCALASE containing an d" 1.5 Anson's haemoglobin method units/gram 0. 6 0. 6 w Sfilt'h ldryl conitaiiiirig compgund).

c ea c ;,g gf gf g g g ffig j fffffi{{ ?ff (a) (a) Stained swatches were soaked according to procedure B l A J G Ph 1 l 22 79 using detergent composition (b) containing cysteine as activanons, 011111. en. 5 O 1 Indicated with GO1T8SDOiding stain removal results. The reflecf'ance refldmgs w y y the cleanmg W E L ELWZ synergism obtained by incorporating an activator into an enzyme containing detergent composition. These detergent formulations are used for preparing soaking and laundering solutions with a 0.5 percent product concentration 2 5 TABLE I a water hardness of 20 grains/U.S. gallon. stain removal (12% Test swatches (cotton) stained with any of the following I df l Without 1% of 3% 0f Stammg P use or eva uanons p p Staining solution used activator cysteine cysteine blood-ink-milk Bloodrnilkink 10.5 16.0 18.5 mllk-mk i i niki nk 28.5 42.0 40.0 g -w iteink. 5.0 17.5 27.5 egg wh'te 0050a 10.0 14.5 16. 0 -cocoa g m i i i The blood-ink-milk (Art. 1 l6) and cocoa (Art 1 l2) swatches are supplied by EMPA, St. Gallen. Switzerland. The milk-ink and egg-white-ink staining solutions are prepared by Stained swatches were washed in a T adding a 15 percent aqueous solution of egg-white or milk according to procedure A using detergent composition (powdered or crystalline to a 15 percent aqueous solution of (a) containing cysteine as activator. black drawing ink. "pvhw 5 The swatches are immersed in the solution and passed 40 through a handwringer whereafter they are heated for 20 B E H minutes in 70C. water. TA

The test swatches are then soaked and/or washed thereby ai removal proceeding as follows: without 3% A. The stained swatches are washed for 30 minutes at 45 staining 5011mm used cysteine C. in a washing solution containing the enzymatic deter- Egg-white-ink 25 32 gent composition and the activator. The operation is carg ggg g 2% ried out in a Launder-ometer supplied by Atlas Electric W vow-.. Devices Co., Chicago. Illinois, U.S.A.; or in a Terg-O- tometer" supplied by U.S. Testing company, Hoboken, N.J.,U.S.A. Any of the following examples has been carried out by B. The stained swatches are soaked at ambient temperature washing with egg-white-ink swatches according to procedure for 2 hours in a soaking solution, containing the enzy- A. matic detergent composition and the activator, The detergent formulation used corresponds to (a) of examwhereafter the swatches to be soaked are agitated for 10 pic i wherein the quantities of enzyme preparation have been m nutesvaried esinsi sated- TABLE III Wt. percent of Stain removal (R%) Wt. per- ALCALASE cent of (same as in Without With Example Activator activator Example I activator activator 0.5 0.4 27.5 33.5 1.5 0.4 27.5 42 II Cysteine 3 0.4 27. 5 46 5 0.2 24.5 47 10 0.2 24.5 47 III Cysteinhydrochloride 5 0.4 33 5 10 0.4 33 51.5 IV Thloglycollic acid 5 0.4 24. 5 49 V Thioglycerol 1 0.4 41.5 50 VI- Thioglycollic acid isooctylester 2 0.4 41. 5 56.5 VIL. Thioglycoilic acid dodecylester. 2. 5 0.4 41. 5 47. 5 VIII Thioglycollic acid ethylester. 1. 2 0. 4 39. 5 49. 5 IX Ca-thioglycolate 1 0.4 36.5 4 10 0.4 27 49 Sodium sulfide 0. 6 0.3 31 39 6 0.4 39.5 53

7 8 A detergent composition prepared as described in example I Table -Ebnlinued having the following formula (in weight percent) sulfide 0.6 0.6 25 495 1.2 0.6 1s 5s 'l'etrapropylene benzene sulfonate sodium salt 10 2.4 b 25 56.5 Sodium tripolyphosphate 30 mdium- 3 19 5 26 Condensation product oftallow alcohol with l 1 moles of OJ I95 4 ethylene oxide 4 L2 0.3 1945 36.5 Hydrogenated fatty acids (CM-C") 4 0.6 043 30,5 43 Sodium sulfate l2 Sodium silicate (ratio SiO,/Na,O=2/l 6.0. Enzyme (ALCALASE containing 1.5 Anson: haemoglobin we claim t method units/8,) (M I. An enzyme-containing detergent composition consisting Sodium sulfide Q6 essentially of an organic detergent and an alkaline builder salt Mi cel n l nc to 100 in a ratio of builder salt to detergent of about 20: l to 1:5; was used for the washing of Stained switches accordmg IQ from about 0.01 to about 10 weight percent of the composi- Procedure tion of an enzyme activity-enhancing agent containing one or more sulfhydryl groups and selected from the 'ANSONJoum. Gen. Physiol. 2179 I939) group consisting of cysteine, cysteine hydrochloride, thioglycollic acid, thioglycerol, thioglycollic acid esters of TABLE IV alcohols containing from one to about 16 carbon atoms, thioglycollic acid ethylester, and calcium thioglycolate; Sta' solution 20 and "l a 8 sun Removal (Rm from about 0.005 to about 4 weight percent of a proteolytic enzyme WhlCh does not contain sulfhydryl groups or without activator with 0.6% Na,S dtsulfide bonds. ,wwmwink I 34 2. The detergent composition of claim I wherein the enzyme used is of bacterial origin.

The compositions listed hereafter have been tested as The detergem composition 0f claim 2 wherein the described for examples ll through IX except that the detergent Zyme used obtained from 3 of fformulation used in the first composition corresponds to for- The detergent Composmo" of claim 1 wherein the mulation (b) of example I and the composition used in the zyme 15 present in an amount of from about 0.01 to about 0.2 second composition corresponds to the last composition weight Percent ifi ll i l d 5. The detergent composition of claim I wherein the sulfhydryl beating compound is presen! in 3: amount ofwfrom oto TABLE V m 6: ;E:;gent composition of claim 5 wherzinn'2 g hydryl bearing compound IS P amo eight percent.

R i use about 0.2 to about 2 w Activator sum em 7. The composition of claim 6 wherein the sulfltydryl bear ad or (me a in withou l i compound is cystein Examph activator activator It It I I v 40 .5 lodium- 0.6

2 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION December 14, 1971 5,627,683 Dated Wolfgang Ernst Adam, Alain Hardy, Arnvid Sverre Roald Inv nt and Wahib Nassif Zaki Patent No.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 50, "0.02" should be 0.2

II II Column 2 llne o2, (C C should be (C C Signed and sealed this 1st day of August 1972.

(SEAL) Attest:

ROBERT GU'ITS-CHALK Commissioner of Patents EDWARD M.FLJ:JTCHER,JR- Attesting Officer 

2. The detergent composition of claim 1 wherein the enzyme used is of bacterial origin.
 3. The detergent composition of claim 2 wherein the enzyme used is obtained from a strain of bacillus subtilis.
 4. The detergent composition of claim 1 wherein the enzyme is present in an amount of from about 0.01 to about 0.2 weight percent.
 5. The detergent composition of claim 1 wherein the sulfhydryl bearing compound is present in an amount of from 0.05 to 5 weight percent.
 6. The detergent composition of claim 5 wherein the sulfhydryl bearing compound is present in an amount of from about 0.2 to about 2 weight percent.
 7. The composition of claim 6 wherein the sulfhydryl bearing compound is cysteine. 